CN102335625A - Application of metal formates as combustion catalyst in solid propellant - Google Patents
Application of metal formates as combustion catalyst in solid propellant Download PDFInfo
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- CN102335625A CN102335625A CN2011101989050A CN201110198905A CN102335625A CN 102335625 A CN102335625 A CN 102335625A CN 2011101989050 A CN2011101989050 A CN 2011101989050A CN 201110198905 A CN201110198905 A CN 201110198905A CN 102335625 A CN102335625 A CN 102335625A
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Abstract
The invention discloses application of formates as a combustion catalyst in a solid propellant. The metal formates comprises anhydrous formates or formates containing solvent molecules, which are formates of metals in the s region in the periodic table, formates of metals in the p region, formates of metals in the d region, formates of metals in the ds region or formates of metals in the f region. The formates disclosed in the invention have the highest oxygen content in all carboxylates. Through massive examples, the inventor proves that the formates have better combustion catalytic performance than acetates with similar composition, and thus, can be used as a combustion catalyst in the propellant component.
Description
Technical field
The present invention relates to metal formate as the application of combustion catalyst in solid propellant.
Background technology
Combustion catalyst is to regulate one of indispensable component of SOLID PROPELLANT COMBUSTION performance, is crucial functional material in the solid propellant prescription.For improving the SOLID PROPELLANT COMBUSTION performance,, hope that usually propellant has the wide and low combustion characteristics of pressure index of the fast adjustable extent of combustion, and this combustion characteristics realizes through adding combustion catalyst mainly according to the demand of solid engines steady operation.
Double base propellant and fourth hydroxyl propellant are the one type of high-energy fuel that is used for rocket and guided missile, and its shortcoming is that combustion speed is lower, pressure index is higher, need to add combustion catalyst and regulate combustibility.Amplitude according to improving combustion speed is different, and the combustion catalyst of use is also different.The derivative RF of hydroxyl ferrocene, the ester derivative FBB of ferrocene and multinuclear ferrocene burningrate catalyst GFP can make the combustion speed of fourth hydroxyl propellant (regulate arbitrarily in 6.86 ~ 9.8MPa) scopes at 10 ~ 100 mm/s; Particularly the performance classes of GFP is similar to the hot catalyst of external Kato, is applicable to the fast fourth hydroxyl propellant of the high combustion of development 30 ~ 76 mm/s (6.86MPa).Though ferrocene and derivative thereof can increase substantially propellant burning rate, at present ferrocene is prone to migration in propellant, volatile problem is solved as yet at all, and the costing an arm and a leg of ferrocene and derivative thereof, cost are high, have limited its application.
Before and after the eighties, the foreign scholar has begun the research of transition metal oxide (TMO) to propellant combustion and the influence of AP thermal decomposition performance.People such as Kishore are to Fe
2O
3, Co
2O
3, MnO
2, CoO, Cu
2O studies the thermal decomposition performance of AP and propellant.People such as Santacesaria are also to Co
2O
3, Fe
2O
3, CoO and Co
3O
4Influence to the AP thermal decomposition characteristic is studied.Hermoai and Salmon have studied transition metal oxide MnO
2, CoO and Ni
2O
3Influence to the AP thermal decomposition characteristic.Discover that TMO can catalysis quicken the pyrolysis of AP, thereby improve the combustion speed of AP propellant.
In recent years, complex has obtained broad research as combustion catalyst.Discover that bismuth citrate and 2,4-dihydroxy-benzoic acid bismuth are that double-basis is the good combustion catalyst of propellant, they can significantly improve the combustion speed of double base propellant, and reduce its pressure index, and with mantoquita and a small amount of carbon black compound after, catalytic effect is better.People such as Zhang Heng (fiery explosive journal; 2001; 24 (3): 7-9) with 3-nitrophthalic acid and the zirconyl nitrate 3-nitrophthalic acid zirconium that has been feedstock production, and to have studied it be the influence of propellant burning property to double-basis, finds that 3-nitrophthalic acid zirconium is that propellant combustion has good catalytic action to double-basis; Can obviously improve the combustion speed of propellant low pressure stage; And significantly reduce the burning rate pressure exponent of high pressure section, after itself and mantoquita are compound, can further improve combustion speed and reduce burning rate pressure exponent.(solid-rocket technology, 1999,22 (2): 45-47) also studied a kind of compd B a (NTO) .3H of non-toxic and safe such as Guan Dalin
2The application of O in solid propellant.(energetic material such as Fan Xuezhong; 2007; 15 (4): 316-319.) NTO lead salt and NTO mantoquita can be used for AP (ammonium perchlorate)-CMDB propellant by combustion catalyst as containing, and its catalysis characteristics is studied, it is fast than the combustion under the low pressure (1 ~ 7 MPa) to find that NTO is plumbous, the copper derivative all can improve the AP-CMDB propellant; And make the combustion prompt drop under the higher pressure (10 ~ 20 MPa) low, and the burning rate pressure exponent of propellant is reduced.(solid-rocket technology such as Deng Minzhi; 2003; 26 (3): 53-55) studied the application of tetrazolium salts in containing little cigarette composite modified double-base propellant of RDX, found that the metal lead salt of tetrazolium class has catalytic action preferably, it can reduce the interval pressure index of 6 ~ 10 MPa pressure.(war industry's journal, 2004,25 (1): 30-33) studied the inferior dimethyl tetrazolium lead of 5-, copper and strontium salt, phenyltetrazole lead, copper and strontium salt are as the application of combustion catalyst for Zhao Fengqi etc.
Catalyticing combustion process is the oxidation reaction that combustible and oxygen take place, and the oxygen content height possibly be very important to the raising of energy in the combustion process.The content of oxygen is not high in the existing complex type combustion catalyst, and this may limit its performance of performance in some aspects, and the present invention is conceived to screen high oxygen containing complex type combustion catalyst.
Through calculating, the inventor finds: the oxygen content difference is very big in the carboxylic acid molecules, and table 1 is modal formic acid, malonic acid and the contrast of terephthalic acid (TPA) oxygen content.
Table 1 is visible; Oxygen content in the formic acid molecule is the hat of all carboxylic acids, and up to 69.5%, and the oxygen content of terephthalic acid (TPA) is merely 23.9%; Whether this analysis result enlightenment inventor can synthesize the formic acid complex of rich oxygen content, and it may have outstanding catalytic combustion properties.The inventor does not see relevant report through literature search.
Summary of the invention
The objective of the invention is to screen provides the formates of one type of rich oxygen content combustion catalyst.
Metal formate of the present invention comprises anhydrous formic acid salt or contains the formates of solvent molecule; Metal formate is the formates of s district metal in the periodic table of chemical element, the formates of p district metal, the formates of d district metal, the formates of ds district metal or the formates of f district metal; As: lithium formate, sodium formate, potassium formate, magnesium formate, calcium formate, strontium formate, barium formate, lead formate, formic acid tin, formic acid bismuth, formic acid antimony, formic acid manganese, chromic formate, ferric formate, cobaltous formate, nickel formate, copper formate, zinc formate, formic acid cadmium, formic acid lanthanum, cesium formate, formic acid praseodymium, formic acid neodymium etc. are preferably barium formate, lead formate, formic acid tin, formic acid bismuth, chromic formate, ferric formate, cobaltous formate, nickel formate, copper formate, formic acid lanthanum, cesium formate; What said solvent molecule was common is water, methyl alcohol, ethanol, propyl alcohol or acetonitrile etc.
Formates disclosed by the invention has the highest oxygen content in all carboxylates, the inventor shows through a large amount of illustrations, compares with forming approximate acetate, and formates has more outstanding combustion catalysis performance, can be used as the combustion catalyst in the propellant component.
Description of drawings
Fig. 1 Coordination Polymers particulate [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) the X-ray powder diffraction pattern of (1);
Fig. 2 Coordination Polymers particulate [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) infrared spectrogram;
Fig. 3 Coordination Polymers particulate Co
2(HCOO)
4(H
2O)
4] the X-ray powder diffraction pattern of (2);
Fig. 4 Coordination Polymers particulate [Co
2(HCOO)
4(H
2O)
4] infrared spectrogram;
Fig. 5 Coordination Polymers particulate [Ni
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) the X-powder diagram of (3);
Fig. 6 Coordination Polymers particulate [Ni
2(HCOO)
4(H
2O)
4] the X-ray powder diffraction pattern of (4);
The SEM photo of Fig. 7 Coordination Polymers particulate (1)-(4), wherein A Coordination Polymers particulate (1); B Coordination Polymers particulate (2); C Coordination Polymers particulate (3); D Coordination Polymers particulate (4);
The X-ray powder diffraction pattern of Fig. 8 Coordination Polymers particulate (1) and (2) thermal decomposition product;
The X-ray powder diffraction pattern of the thermal decomposition product of Fig. 9 Coordination Polymers particulate (3) and (4);
The DSC curve of Figure 10 Coordination Polymers particulate (1) catalysis AP thermal decomposition;
The DSC curve of Figure 11 Coordination Polymers particulate (2) catalysis AP thermal decomposition;
The DSC curve of Figure 12 Coordination Polymers particulate (3) catalysis AP thermal decomposition;
The DSC curve of Figure 13 Coordination Polymers particulate (4) catalysis AP thermal decomposition;
The DSC curve of thermal decomposition product catalysis AP thermal decomposition in Figure 14 Coordination Polymers particulate air;
The DSC curve of Figure 15 nickel acetate/cobalt catalysis AP thermal decomposition;
The X-ray powder diffraction pattern of Figure 16 lead formate;
The DSC curve of Figure 17 lead formate catalysis AP thermal decomposition;
The X-ray powder diffraction style of the lead formate that Figure 18 synthesizes and standard card contrast;
The DSC curve of Figure 19 copper formate catalysis AP thermal decomposition.
The specific embodiment
Embodiment 1 [M (HCOO)
2Guest]
n(M=Co
2+, Ni
2+) Coordination Polymers particulate synthetic
1, [Co (HCOO)
2Guest]
nSynthesizing of Coordination Polymers particulate
(1) [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) (1) is synthetic
Take by weighing the CoCl of 0.36g
26H
2O (0.0015mol) is dissolved in the 5ml methyl alcohol, and ultrasonic 20min gets solution A; 0.46g (0.01mol) formic acid mixes with 0.67g (0.66mol) triethylamine, the methanol solution that is dissolved in 12ml forms solution B; Solution B is slowly added in the solution A, and ultrasonic 30min forms mixed liquor, further mixed liquor is transferred in the microwave reaction system and reacts, and setting reaction temperature is 120 ℃, and the time is 20min.After reaction finished, temperature was reduced to room temperature, sample is taken out centrifugal, with methanol wash for several times after, natural drying at room temperature obtains pink powder.Results of elemental analyses: theoretical value is (mass percent): C:17.48, H:2.51.Experiment value is (mass percent %): C:17.67, H:2.34.
(2) [Co
2(HCOO)
4(H
2O)
4] (2) synthetic
With [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) synthesis condition of (1) is similar, and difference is to change solvent methanol into ethanol.Results of elemental analyses: theoretical value is (mass percent %): C:12.98, H:3.27; Experiment value is (mass percent %): C:12.69, H:3.58.
2, [Ni (HCOO)
2Guest]
nSynthesizing of Coordination Polymers particulate
(1) [Ni
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) (3) are synthetic
With 0.36g (0.0015mol) NiCl
26H
2O is dissolved in ultrasonic 20min formation solution A in the 5ml methanol solution, 0.46g (0.01mol) formic acid is mixed and is dissolved in 12ml methyl alcohol getting solution B with 0.67g (0.66mol) triethylamine, and solution B is slowly added in the solution A, continues ultrasonic 30min; Set reaction temperature and be respectively 120 ℃ and 20min with the time, in the microwave reaction system, react above-mentioned mixed solution, the reaction temperature that finishes is afterwards reduced to room temperature, sample is taken out centrifugal, the methanol wash several, drying at room temperature obtains Coordination Polymers particulate (3).Results of elemental analyses: theoretical value is (mass percent): C:16.94, H:2.44; Experiment value is (mass percent %): C:17.01, H:2.63.
(2) [Ni
2(HCOO)
4(H
2O)
4] (4) synthetic
With [Ni
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) reaction condition of (3) is similar, and difference is to change solvent methanol into ethanol, and reacting resultant sample is Coordination Polymers particulate (4).Results of elemental analyses: theoretical value is (mass percent %): C:13.00, H:3.27.Experiment value is (mass percent %): C:13.06, H:3.27.
(1) [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) X-ray powder diffraction
The X-ray powder diffraction style of Coordination Polymers particulate (1) is as shown in Figure 1, and its baseline is more flat, and diffraction is stronger, and the peak type is sharp-pointed, and slightly wideization shows that the complex crystal degree is higher, is crystalline products.The powder diffraction peak of Coordination Polymers particulate (1) is identical with the match powder diffraction peak position of known formates complex (RAVVIU) in the CCDC database, intensity is suitable; This explanation Coordination Polymers particulate (1) is identical with the frame structure of known formates complex (RAVVIU); In conjunction with results of elemental analyses, infer that Coordination Polymers particulate (1) consists of [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O).
(2) [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) infrared spectrum analysis
Adopt pellet technique, utilize Fourier's infrared spectrometric analyzer in the 400-4000 scope, Coordination Polymers particulate (1) to be carried out infrared spectrum analysis (as shown in Figure 2).Because the HCOO in the formic acid
-Be a polyelectron conjugated system, the vibration coupling of two C=O makes it two stronger absworption peaks occur, and wherein, the antisymmetric stretching vibration absworption peak is at 1610-1560cm
-1In the scope; The symmetrical stretching vibration absworption peak is at 1440-1360 cm
-1In the scope.The infared spectrum of Coordination Polymers particulate (1) shows that Coordination Polymers particulate (1) is 1555 cm in wave number
-1With 1369 cm
-1There is strong absworption peak these two positions, at 1555 cm
-1The strong absworption peak at place is the antisymmetric stretching vibration absworption peak of carboxyl, at 1369 cm
-1The absworption peak at place is the symmetrical stretching vibration absworption peak, and through calculating, the difference DELTA ν of two stretching vibration absworption peak wavelength (being the wavelength-symmetrical stretching vibration peak at antisymmetric stretching vibration peak) is 186 cm
-1, this Δ ν value is at 175-205 cm
-1Scope in, this has explained that the oxygen in the carboxyl is the pattern coordination of two monodentate bridgings.Also there is a strong broad peak at 3200 places in infrared spectrogram, and this peak is the hydroxyl peak of solvent molecule water in the complex.
(3) [Co
2(HCOO)
4(H
2O)
4] the X-ray powder diffraction
To complex [Co
2(HCOO)
4(H
2O)
4] X-ray powder diffraction style and CCDC database in the diffraction maximum position consistent (like Fig. 3) of match collection of illustrative plates of known complex (COFORM01); Infer that Coordination Polymers particulate (2) and known formates complex (COFORM01) have the identical frames structure; In conjunction with results of elemental analyses, infer that Coordination Polymers particulate (2) consists of [Co
2(HCOO)
4(H
2O)
4].
(4) [Co
2(HCOO)
4(H
2O)
4] infrared spectrum analysis
Simultaneously, further Coordination Polymers particulate (2) is carried out infrared spectrum characterization (like Fig. 4), Coordination Polymers particulate (2) is at wave number 3347 cm
-1The position a very strong broad peak is arranged, analyze theoretically, the ν of water appears in the stretching vibration meeting of proton in the water in the stretching vibration zone of hydroxyl
O-HDate at 3400 cm greatly
-1The position and the ν in the carboxyl appears
O-HAt 3200-2500 cm
-1Scope in also can produce broad peak, and this is absorbed in 2700-2500 cm
-1Have small peak through regular meeting, so the strong wide absworption peak of here this is the coefficient result of O-H in water of coordination and the carboxyl.In infrared spectrogram, be 1379 cm simultaneously in wave number
-1Place and 1575 cm
-1A more intense absworption peak has appearred respectively in the place, at 1379 cm
-1The strong absworption peak at place is the symmetrical stretching vibration peak of carboxyl, at 1575 cm
-1The strong absworption peak at place is the antisymmetric stretching vibration peak of carboxyl, and these two peak-to-peak difference DELTA ν of stretching vibration are 196 cm
-1, difference is at 175-205 cm
-1In the scope, infer that the carboxyl in the Coordination Polymers (2) is with the coordination of two monodentate bridging coordination mode.
(5) [Ni
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) X-ray powder diffraction
The XRD style of Coordination Polymers particulate (3) is as shown in Figure 5; Coordination Polymers particulate (3) is consistent with the diffraction maximum position of the match collection of illustrative plates of the known formates complex of CCDC database (XOBXIW); Therefore can infer that both frame structures are identical; In conjunction with results of elemental analyses, infer that Coordination Polymers particulate (3) is [Ni
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O).Its ir data and [Co
6(HCOO)
12] 2 (CH
3OH) 2 (H
2O) infrared spectrogram result is similar.
(6) [Ni
2(HCOO)
4(H
2O)
4] the X-ray powder diffraction
Diffraction maximum position to the match collection of illustrative plates of formates complex (NIFORM) known in the XRD style of Coordination Polymers particulate (4) and the CCDC database is consistent; Intensity is (Fig. 6) quite; In conjunction with results of elemental analyses, infer that Coordination Polymers particulate (4) is [Ni
2(HCOO)
4(H
2O)
4].Its ir data and [Co
2(HCOO)
4(H
2O)
4] infrared spectrogram result similar.
(7) microscopic appearance of Coordination Polymers particulate (1)-(4)
It is as shown in Figure 7 that ESEM (SEM) photo is carried out in Coordination Polymers particulate (1)-(4); Coordination Polymers particulate (1) presents the nano-micrometre hierarchy; Diameter is that the microballoon of 1-2 μ m assembles (shown in Fig. 7 A) by the nano particle of 50-100nm; The Coordination Polymers particulate (2) that in alcohol solvent, synthesizes is a hexagon in the form of sheets, the about 5 μ m of its length of side, the about 1 μ m of thickness (shown in Fig. 7 B).Obtaining Coordination Polymers particulate (3) in the methanol system is to be approximately 1 μ m micro-spherical particle (shown in Fig. 7 C), and through in alcohol solvent, obtain Coordination Polymers particulate (4) for length be 5 μ m, the cuboid of wide and high about 2 μ m.(shown in Fig. 7 D).It is thus clear that different solvents not only influences complex structure, simultaneously also highly significant ground has influenced the pattern and the size of complex.
(8) heat endurance of Coordination Polymers particulate (1)-(4)
The TG curve map of Coordination Polymers particulate (1)-(4) room temperature to 500 ℃ shows that four kinds of Coordination Polymers particulates lose solvent molecule fully before 150 ℃, do not contained the complex of solvent molecule.
The sign of embodiment 3 Coordination Polymers particulates (1)-(4) air thermal dissociation product
Under air atmosphere, thermal decomposition is carried out in 500 ℃ in synthetic Coordination Polymers particulate (1)-(4) in tube furnace, to calcine 4 hours, the XRD analysis of Coordination Polymers particulate (1) and (2) thermal decomposition product is indicated as Co
3O
4(Fig. 8), corresponding to JCPDS card 42-1467.
The XRD analysis of Coordination Polymers particulate (3) and (4) thermal decomposition product is indicated as NiO (Fig. 9), corresponding to JCPDS card 47-1049.
Ammonium perchlorate is a kind of important propellant component; The corresponding oxide catalysis AP thermal decomposition that Coordination Polymers particulate that this enforcement prepares embodiment 1 and thermal decomposition obtain is studied; The discovery formates is compared with corresponding oxide, can significantly improve the thermal discharge of AP.
Experimentation and condition are following: by sample and AP mass ratio is that 1:3 carries out weighing (the about 6mg of AP, the about 2mg of sample), makes sample and AP fully mix the laboratory sample of back for making the two mixed grinding; Amount of samples during test: 0.5-1.0mg; Heating rate: 10 ℃/min; Temperature range: 30-490 ℃; Atmosphere: still air atmosphere.
(1) Coordination Polymers particulate (1) to (4) catalysis AP thermal decomposition result
Shown in Figure 10-13; Coordination Polymers particulate (1) to (4) two thermal decomposition stages (low-temperature decomposition stage and pyrolytic stage) that AP is original have been transformed into a thermal decomposition stage; And emitted great amount of heat, thermal discharge is respectively 1.47,1.73,1.48 and 1.91kJ/g.
(2) Coordination Polymers particulate (1)-(4) aerial thermal decomposition product is to the thermal decomposition of AP
The thermal decomposition product catalysis AP thermal decomposition (Figure 14) that embodiment 3 prepares, corresponding thermal discharge difference 0.65,0.63,1.06 and 0.97kJ/g.
Show that through above-mentioned contrast the formates complex is compared reduction and the increase of AP apparent heat of decomposition that corresponding oxide more helps the pyrolytic peak of AP, it can be used as the propellant combustion catalyst.
The inventor has further studied and the acetate catalysis AP thermal decomposition behavior of formiate like composition, and is shown in figure 15, uses corresponding acetate, and the cobalt acetate thermal discharge is 0.76kJ/g, and the nickel acetate thermal discharge is 0.17kJ/g.
The result shows that similar although formates and acetate are formed, its catalysis AP thermal discharge is low significantly.
Embodiment 6 lead formates synthetic and to the catalytic decomposition behavior of AP
Similar with the synthetic method of embodiment 1; Different is that slaine uses lead acetate, and the consumption of triethylamine doubles, and the XRD style of the Coordination Polymers particulate for preparing is shown in figure 16; Can be retrieved as lead formate (JCPDS card 14-0825) fully; Decompose fully before thermogravimetric analysis under the air atmosphere shows 300 ℃, catalysis AP thermal decomposition (Figure 17) shows that its thermal discharge is 1.45kJ/g, and the thermal discharge of lead acetate is merely 0.71kJ/g.
Take by weighing 9.4 gram copper sulphate and 7.2 gram sodium acid carbonates, levigate and mix in the mortar, under agitation mixture slowly is added in the nearly boiling distillated water of 100mL; Heat a few minutes, leave standstill to the clarification of upper strata liquid, with decantation separation solution and deposition; Washing precipitation to sulfate radical-free (checking) with barium chloride; In deposition, add 10mL distilled water, about heated and stirred to 50 ℃, dropwise add the dissolving fully of an amount of formic acid to deposition.Solution is evaporated to about 1/3 (about 10mL) of original volume, is cooled to filtration under diminished pressure after the room temperature, with small amount of ethanol washing crystal twice, suction filtration is to doing again, products C u (HCOO)
2.4H
2O.Its XRD style is shown in figure 18, can be retrieved as copper formate (JCPDS card 32-0332) fully, and catalysis AP thermal decomposition (Figure 19) shows that its thermal discharge is 1.02kJ/g, and the thermal discharge of Schweinfurt green is merely 0.53kJ/g.
Synthesizing of embodiment 8 alkali metal and alkaline-earth metal formates
The method of the synthetic employing acid-base neutralization of alkali metal and alkaline-earth metal formates adds to formic acid in alkali metal and the alkaline earth metal hydroxide, and evaporation and concentration can obtain corresponding alkali metal and alkaline-earth metal formates.Catalysis AP result shows that the thermal discharge of formates (potassium formate, barium formate) catalysis AP is about a times of respective metal acetate.
Claims (6)
1. metal formate is as the application of combustion catalyst in solid propellant.
2. according to the said application of claim 1, metal formate comprises anhydrous formic acid salt or contains the formates of solvent molecule.
3. according to the said application of claim 2, said solvent molecule is water, methyl alcohol, ethanol, propyl alcohol or acetonitrile.
4. according to the said application of claim 1, metal formate is the formates of s district metal in the periodic table of chemical element, the formates of p district metal, the formates of d district metal, the formates of ds district metal or the formates of f district metal.
5. according to the said application of claim 4, metal formate is anhydrous or contains the lithium formate of solvent molecule, sodium formate, potassium formate, magnesium formate, calcium formate, strontium formate, barium formate, lead formate, formic acid tin, formic acid bismuth, formic acid antimony, formic acid manganese, chromic formate, ferric formate, cobaltous formate, nickel formate, copper formate, zinc formate, formic acid cadmium, formic acid lanthanum, cesium formate, formic acid praseodymium, formic acid neodymium.
6. according to the said application of claim 5, metal formate is anhydrous or contains the barium formate of solvent molecule, lead formate, formic acid tin, formic acid bismuth, chromic formate, ferric formate, cobaltous formate, nickel formate, copper formate, formic acid lanthanum, cesium formate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111062A (en) * | 2015-08-19 | 2015-12-02 | 西安近代化学研究所 | 1,4,5,8-tetrahydroxy anthraquinone magnesium compound and preparation method therefor |
| CN105777458A (en) * | 2014-12-26 | 2016-07-20 | 比亚迪股份有限公司 | Automatic ignition powder for gas generator of air bag restraint system of automobile and preparation method of automatic ignition powder |
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| CN113929919A (en) * | 2021-09-26 | 2022-01-14 | 西安近代化学研究所 | Ni and Ba bimetal MOFs, preparation method and application |
| CN114276850A (en) * | 2021-12-24 | 2022-04-05 | 安徽工业大学 | Fluorine-doped graphene-loaded Pb composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513596A (en) * | 2003-07-07 | 2004-07-21 | 深圳大学 | Nano-copper-lead composite oxide powder and its preparation method |
| CN101440008A (en) * | 2007-11-23 | 2009-05-27 | 深圳大学 | Lead oxide / carbon nano-tube composite powder and preparation thereof |
-
2011
- 2011-07-15 CN CN201110198905.0A patent/CN102335625B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513596A (en) * | 2003-07-07 | 2004-07-21 | 深圳大学 | Nano-copper-lead composite oxide powder and its preparation method |
| CN101440008A (en) * | 2007-11-23 | 2009-05-27 | 深圳大学 | Lead oxide / carbon nano-tube composite powder and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| 付小龙等: "铅盐对高能无烟改性双基推进剂燃烧性能的影响", 《含能材料》, vol. 15, no. 4, 31 August 2007 (2007-08-31), pages 329 - 330 * |
| 宋秀铎等: "2，4-二羟基苯甲酸铋对双基推进剂燃烧的催化作用", 《火炸药学报》, vol. 29, no. 1, 28 February 2006 (2006-02-28), pages 38 - 39 * |
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